DD140456A5 - PROCESS FOR PREPARING 3- (N-ACYL-N-ARYLAMINO) -GAMMA BUTYROLACTONES AND GAMMA BUTYROTHIOLACTONES - Google Patents

Description

The invention relates to a process for the preparation of the title compounds, which can be used in agriculture as fungicidal agents.

Well-known technical solutions

U.S. Patents 3,933,860 and 4,012,519 disclose the use of a large amount of ^- (N-acyl-N-arylaminoi-lactones and 3- (N-acyl-N-arylamino) - Lactams described as protective fungicides

In U.S. Patents 4 034 108 and 4 * "015" 648 is the use of! N- (Mathoxycarbonylethyl) -U ~ halogenacetylanilinen as fungicides for prevention and treatment described * The DT-OS ^f s 2 * 643 »403 and 2 * 643 * 445 describe the use of 3 \ ^T - (alkylthiocarbonylethyl) acetanilides for the control of fungi, in particular fungi of the families Phycomycetes.

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In the IJL-OS 152.849 the use of N- (alkoxy, methyl) -acetaniliden as fungicides is described.

Object of the invention

It is an object of the invention to enrich the state of the art with new effective fungicides.

Essence of the invention

It has now been found that 3- (N-acyl-1-t-arylamino) ·

t ^ -butyrpacetic acid and butyrothiolactones for controlling fungi, in particular the Downy Mildew fungal infection, which is due to a fungus of the family Peronosporaceae, and the late blight fungal infection caused by Phytophthora infestans , Some of the compounds of the invention are useful as both preventative fungicides, i. H. they prevent or protect against fungal infections, and as eliminating fungicides, d. H. they effectively eliminate and heal the resulting infections. The compounds of the invention are especially preferred for controlling grape downy mildew (grape downy mildew).

The invention provides 3- (II-ACYL-U-ARYLAMIlTO) -. BUTYROLACTONE or - ^ BUTYROTHIOLACTOKE the general

Formula I

Do not

^ .CR ¹

liCT (I)

CHOCH ₀

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which are characterized in that Ar represents a phenyl or TTaphtyl group, which are optionally identical or different with fluorine, chlorine, bromine atoms, alkyl groups having 1-4 carbon atoms or alkoxy groups substituted with 1-4 carbon atoms, R is a hydroxymethyl group, a Halomethyl group having 1-3 identical or different fluorine, chlorine or bromine atoms, an alkoxymethyl group having 1-6 carbon atoms, Alkylthio'methylgruppe having 1-6 carbon atoms; Phenylthiomethyl group, phenoxymethyl group, a phenylthiomethyl or phenoxymethyl group which on the phenyl ring with 1 or 2 fluorine atoms, chlorine atoms, bromine atoms, alkyl groups having 1-4 carbon atoms or alkoxy groups having 1-4 carbon atoms

atoms are the same or different substituted, R represents a hydrogen atom, a chlorine atom, bromine atom, an alkyl group having 1-6 carbon atoms or a phenyl group optionally substituted with 1 or 2 fluorine atoms, chlorine atoms, bromine atoms or alkyl groups having 1-6 carbon atoms the same or different and Y represents an oxygen atom or a sulfur atom with the proviso that Y is not an oxygen atom when Ar is a phenyl group or a substituted phenyl! methy! group is.

represents a substituted phenyl group and R is a halogenated

Examples of substituted phenyl groups which Ar may represent are the 2-fluorophenyl, 2,4-dichlorophenyl, 3,5-dibromophenyl-j 4-methylphenyl, 2,6-diethylphenyl, 4-methoxyphenyl, 4 ~ Mtrophenyl- ,. 2,6-dimethyl-4-ehlorophenyl, 2,3,6-trimethylphenyl and the 2,3,5,6-tetra-r

t -

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methylphenyl. Preferred substituted phenyl groups, which may be Ar, have as identical or different substituents one or two chlorine atoms, bromine atoms, alkyl groups having 1 to 4 carbon atoms or alkoxy groups having 1-4 carbon atoms. The most preferred substituted phenyl groups are the 2,6-dialkylphenyl group, especially the 2,6-dimethylphenyl group.

Examples of substituted naphthyl groups of the meaning Ar are the 1-naphthyl, 2-naphthyl, 1-methyl-2-naphthyl, 4-methyl-2-naphthyl, 4-methyl-1-naphthyl, 2 Chloro-1-naphthyl, 2-methoxy-1-naphthyl, 2,4-dimethyl-1-naphthyl and the 2,7-dimethyl-1-naphthyl group. Preferred substituted naphthyl groups of the meaning Ar are the 2-alkyl-1-naphthyl groups, in particular the 2-methyl-1-naphthyl group.

Specific examples of halomethyl groups which R can represent are the fluorins of 1-, chloromethyl, bromomethyl, dichloromethyl, tribromomethyl and fluorodi-chloromethyl. As the halomethyl group, the

R is chloromethyl, is preferred.

Specific examples of alkoxymethyl groups of the meaning R are the methoxymethyl, ethoxymethyl, isopropoxymethyl and the n-Pentoxymethy1 group. Preferred as Alkoxymethy1 group of meaning R is the Methoxymethy! Group.

Specific examples of alkylthiomethyl groups of the meaning R are the methylthiomethyl, n-propylthiomethyl

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and the n-phenylthiomethyl group «

Examples of substituted phenylthiomethyl groups and substituted phenoxymethyl groups in the meaning of R are the 4-chlorophenylthiomethyl, 4-methylphenoxymethyl, 2,4-dichlorophenoxymethyl, 3, 5-dimethylphenylthiomethyl and the 2-chloro-4-methylpheno-3-cyanoethyl groups ,

Specific examples of alkyl groups in the meaning of R are the methyl, ethyl, isopropyl and the n-hexyl group. Examples of substituted phenyl groups in the meaning of R are the 2-chloro-phenyl, 2,4-dichlorophenyl, 4-methylphenyl and the. 2,3-dimethyl-phenyl group.

Preferably, Ar is a phenyl group which is the same or different substituted by 1 or 2 fluorine atoms, chlorine atoms, bromine atoms or alkyl groups having 1 to 2 carbon atoms or 2-alkyl-1-naphthyl groups. Most preferred Ar groups are 2,6 Dimethylphenyl group or the 2-methyl-1-naphthyl group.

Preferably, R is an alkoxymethyl group of 1-6 carbon atoms, a chloromethyl or bromomethyl group. Most preferred as the radical R is the methoxymethyl or chloromethyl group

ρ R is the hydrogen atom or a methyl group.

The Ϊί-phenylamino and U-substituted phenylaminothiolactones of the invention may be represented by the general formula II. '

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Il

.CR ¹

Λ (II)

TiH CH ₂

.CH-R ²

in which Ar represents a phenyl group or a substituted phenyl group, as explained above.

1 2 tert, and R and R also have the above significance. In the formula II, Ar preferably represents a phenyl group which is substituted identically or differently with 1 or 2 fluorine atoms, _s chlorine atoms, bromine atoms, alkyl groups with 1 carbon atoms or alkoxy groups with 1-4 carbon atoms.

Preference is given to U-phenylamino and N-substituted pheny1-aminothiolactones of the general formula III

(III) 2

CH-R

R is a chloromethyl group or an alkoxymethyl group having 1-4 carbon atoms, R is the hydrogen atom or methyl group, and R 'and R' are each the same

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Methyl or ethyl group. Particularly preferred are the compounds of general formula III, in

1 2

the R is the chloromethyl or methoxy methyl group, R

4 5

the hydrogen atom and R and R are each the methyl group.

The U-phenylamino and N-substituted phenylminolactones of the invention are represented by the general formula IY ,.

(IV)

I o

O = C ..

in the Ar a phenyl group or substituted phenyl

R 1 is also the above-defined meaning and R is the hydroxymethyl group, alkoxymethyl group having 1 to 6 carbon atoms, alkylthiomethyl group, phenyl thiomethyl group, phenoxymethyl group or the phenylthiomethyl group or phenoxymethyl group which is substituted on the phenyl ring by 1 or 2 Fluorine atoms, chlorine atoms, bromine atoms, alkyl groups having 1 to 4 carbon atoms or alkoxy groups having 1-4 carbon atoms are the same or different substituted.

Preference is given to N-phenylamino- and U-substituted phenylamino-lactones of the general formula V

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O = C

CH-R '

(V)

in which R is an alkoxymethyl group having 1-4 carbon atoms, R is the hydrogen atom or the methyl group and R and R are each the methyl or ethyl group.

interpret. Preference is given to the compounds of the Pormel V,

1 2

in R the methoxymethyl group, R is the hydrogen atom and R and R are each the methyl group.

The ir-iTaphthylamino- and N-Substituted Naphthylamine Lactones and -thiolactones of the Invention may be represented by the general formula VI

Il

CR ¹

CH-

O = C

CH,

CH-R '

(VI)

wherein Ar represents a naphthyl group or a substituted naphthyl group, and R, R and Y have the same meaning as mentioned above. Preference is given to the N-naphthyl

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ιϊηά N-Naphthy! - "Substituted Aminolactones and -thiolactones of the general formula VII

(VII)

CH-R '

in which R is the chloromethyl group, bromomethyl group or alkoxymethyl group having 1-4 carbon atoms, R 7 is the hydrogen atom or an alkyl group having 1-3 carbon atoms and Υ is the oxygen atom or the sulfur atom. Particularly preferred are the compounds

⁵ the chloromethyl group or \ ^J the methyl group and Y the

of formula VII in which R is an alkoxymethyl group, oxygen atom *

Specific examples of the compounds of general formula I include:. · '·

3 - (N-bromo-ethyl-1-phenyl-amino) -. ^ - butyrothio-lactone, 3- (1-isopropoxyacetyl-N- "4-chlorophenylamino) -r-butyrothiolactone,

3 "- (N-phenoxy-3-acetyl-4-methoxyphenylamino) -butyrothiolactone,

3- (N-chloroacetyl-H-2,6-dimethy-phenylamino) -5-niethyl-1-butyrothiolactone,

3- (U ~ dichloroacetyl-Ä ^T ~ 2 ₅ 6-dimethylphenylamino) - υ- butyrothiolactone,

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3- (U-hydroxy-acetyl-N-3-4-dime-thyphenylamino) -f . -butyrothiolacton,

3 - (] J-chloroacetyl-Tr-4-methyl-phenylamino) -5-chloro- γ- butyrothiolactone,

3- (N-hydroxyacetyl-H-2-methoxyphenylamino) -v * -butyrolactone,

3- (H-chloroacetyl-1-2-methylnaphth-1-ylamino) -5-phenyl-γ-butyrothiolactone,

3- (H-methoxyacetyl-N-2-methylnaphth ~ 1-ylamino) -butyrothiolacton,

3- (W-chloroacetyl-K'-1-naphthylamino) -5-methyl- / - -butyrothiolactone,

3- (N-hydroxyacetyl-N-2-methylnaphth-1-ylamino) - γ- - butyrolactone and

3- (N-acetoxyacetyl-H-2-ethylnaphth-1-ylamino) - > butyrolactone.

The lactones and thiolactones of the invention may thus be prepared by ~ / ~ butyrolactone an aniline of the general formula VIII with einemo <-Ha3.ogen or OC halo-f alkylated -butyrothiolacton of the general formula IX and then the o <- (N-arylamino) - ^ "- butyrolactone or butyrothiolactone of the general formula X acylated with an acyl halide of the general formula XI, as product 3- (N-acyl-U-arylamino) - butyrolactone or butyrothiolactone of the general formula I. This reaction is described in the following scheme,

CiI ₀

p ⁽¹⁾

CH-ir

ArM2 + X-CH ¹ 2 CH-R ^ base Ar-IH-CH 1 (X) (VIII) O = C y (IX) -HX O = C I

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Ar-KH-CH - CH ₀ ^M ₁ I ^ά + XCR

(X)

(I)

in which Ar, R, R and Y are as defined above and X is the chlorine or bromine atom.

The alkylation reaction (1) is carried out in the presence of a base "Suitable bases include inorganic alkali metal carbonates, such as potassium carbonates or Uatriumcarbonate _s or organic amines such as trialkylamines, for example triethylamine, or 'pyridine compounds, for example pyridine or 2,6-dimethylpyridine. In general, substantially equimolar amounts of the compounds of general formula VIII and IX and the base are used. In a modified reaction, the aniline compound of general formula VIII is used in molar excess as the base and no additional additional base used. The reaction is carried out in inert organic solvents, for example polar aprotic solvents, such as dimethylformamide and acetonitrile, and aromatic hydrocarbons, such as benzene and toluene. luol, at temperatures of 25 = 150 ⁰ C, preferably 50 ⁰ C to 150 ⁰ C performed »water can be used as a co-solvent. The reaction pressure can be normal pressure, overpressure or negative pressure. For a simple and easy implementation of the reaction, however, normal pressure is generally used. The reaction time

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Of course, depends on the reactants and the reaction temperature. In general, the reaction time is 0.25 to 24 hours. The product of the formula X is generally purified by conventional methods, for example by extraction, distillation or crystallization, before it is used in the acylation reaction (2). The preferred alkylation. Conditions are described in more detail in US Pat. No. 847,503. This application is entitled "Alkylation of Aniline with a Iactone in the Presence of Water". The alkylation reaction (2) is carried out according to usual conditions. The reactants of the general formula X and XI are substantially equidistant "molar amounts in an inert organic solvent at a temperature of 0 -. 100 ⁰ accommodated C into contact to be inserted inert organic solvents include ethyl acetate, methylene chloride, dimethoxyethane, benzene, etc. The product obtained is separated and purified by conventional methods, for example by extraction, distillation, chromatography or crystallization.

In the preparation of a butyrolactone product, (compound of general formula I in which Y represents the oxygen atom), an organic amine, for example a trialkylamine or a pyridine compound, may be employed as the acid acceptor Formula Γ, in which Y represents the sulfur atom), however, no organic amine should be used «

The preferred acylation reaction conditions are

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described in more detail in US Pat. No. 847,504 entitled "Acylation of Lactone-Substituted Aniline Compounds in the Absence of an Acid Acceptor".

The compound of general formula I in which R represents an alkylthiomethyl, phenylthiomethyl, or substituted phenylthiomethyl group may be prepared from the corresponding compound in which R represents a halomethyl group by reacting the corresponding halomethyl compound with an alkali metal mercaptide conventional methods, as indicated in the following equation (3) reacted.

0 C-CH ₀ X

In this equation, Ar, R, X and Y are as defined above, M is an alkali metal, R is an alkyl group or an optionally substituted phenyl group. In the reaction equation (3), Y is preferably the oxygen atom *

The compound of the general formula I, in which R represents a hydroxymethyl group and Y represents the oxygen atom, can be prepared by treatment of the corresponding compounds,

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in which R represents a halomethyl group, with an inorganic alkali metal hydroxide, for example aqueous sodium hydroxide, are prepared. The compound of the general formula I in which R represents the hydroxymethyl group and Y represents the oxygen atom or the sulfur atom can be prepared by hydrolysis of the corresponding compound in which R represents an alkanoyl methyl group.

The compound of general formula I in which R represents a chlorine atom or a bromine atom can generally be prepared by reacting the corresponding

2 -thene compound in which R represents the hydrogen atom, with a chlorinating or brominating agent, such as IT bromosuccinimide or N-chlorosuccinimide, by conventional methods, as shown in the following equation (4), chlorinated or brominated,

0 0 -p

It is 1 OCTJ

C-CH ₂ .CR ^{1 0H}

I - »Ar-UN. +

C-CH ₀ CH - CH ₀ C-CH

it ^ j I ^ »

° O = C CH-X °

y (4)

In this equation, Ar, R, Y and Σ are as defined above.

The compounds according to the invention can be used for controlling fungi, in particular fungal infections on plants. However, some fungicidal agents of the invention may be more fungicidally effective than other antifungal agents.

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on specific types "For example, the activity of preferred compounds of the invention is highly specific to certain fungal diseases, such as downy mildews, for example, Plasmop.ara viticola (grapevine) and Peronospora parasitica (cabbage and cabbage of the name Brassica oleracea (collard)) (late blights), for example Phytophthora infestans (tomato and potato), and cabbage or flower rot and root rot, for example Phytophthora.

The compounds of the invention are particularly valuable fungicides because they cure already existing fungal infections. This allows an economical use of the fungicides according to the invention, since they do not have to be applied to plants, as far as a fungal infection actually does not take place. As a result, a preventive measure, namely the application of fungicides to a possible fungal infection, is not necessary «

When the compounds of the invention are used as fungicides, they are applied in a fungicidally effective amount to the fungi and / or their habitats, such as host plants and non-plant hosts, for example animal products. Of course, the amount employed depends on several factors, for example the host, the type of fungus and the particular compound of the invention. As with most pesticides, the fungicides of the invention are usually not used in concentrated form, but are generally incorporated into common biological inert diluents or carriers. These diluents or carriers are normally used to prepare the dispersion of the active

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fungicidal compounds, taking into account that the formulation and the mode of application may influence the activity of the fungicide. Thus, the fungicides of the invention may be formulated and used as granules, powder fogs, wettable powders, emulsifiable concentrates, solutions, or any of several other known types of formulations, depending on the desired mode of use.

Wettable powders are in the form of finely divided particles which readily disperse in water or other dispersant. These agents usually contain about 5-80% fungicide, balance inert substance. * These inert substances include dispersing agents, emulsifying agents and wetting agents. The powder may be applied to the soil as a dry dust or, preferably, as a suspension in water. Typical supports include Fuller's earth, kaolin clays, silicic acids and other highly absorbent, wettable, inorganic diluents. Typical wetting, dispersing or emulsifying agents include, for example, the aryl and alkylaryl sulfonates and their iso-sodium salts, alkyl-amide sulfonates including the fatty methyltaurides, alkylaryl polyethers. alcohols, sulfated higher alcohols and polyvinyl alcohols, polyethylene oxides, sulfonated animal and vegetable oils, sulfonated petroleum oils, fatty acid esters of polyhydric alcohols and the addition products of ethylene oxide with such esters and the addition products of long-chain mercaptans and ethylene oxide. Numerous other types of useful surfactants are commercially available. When used, the surfactant comprises about 1-15% by weight of the fungicidal agent.

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Powders are present as free-flowing mixtures of the active fungicide with finely divided pesticides, such as talc, efaturtones, kieselguhr ,. Pyrophyllite, chalk, diatomaceous earth, calcihalophosphates, calcium and magnesium carbonates, sulfur, lime, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant. These finely divided solids have a mean grain size of at most about 50 / u. A typical powder formulation useful for the purposes of this invention contains 75 % silica and 25 % toxicant.

Useful liquid concentrates include the emulsifiable concentrates which are homogeneous liquid or pasty agents. These agents can be readily dispersed in water or other dispersant. These emulsifiable concentrates may consist entirely of the fungicide with a liquid or solid emulsifier, or they may also contain a liquid carrier such as xylene, higher nucleated aromatic naphtha products or isophorone, and other non-liquid organic solvents. For use, the concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated.

Other usable formulations of fungicidal types of applications include simple solutions of the "active fungicide in a dispersant in which it is completely soluble at the desired Konsentration such as acetone, alkylated naphthalenes ₉ xylene or other organic solvents. Formulations in the form of granules,

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where the fungicide is on relatively coarse-grained particles are especially useful for airborne distribution or for the penetration of germinated, covered-crop canopy. Pressurized sprays, typically aerosols in which the active ingredient is dispersed in finely divided form as a result of evaporation of a low-boiling dispersible solvent carrier, such as freons, may also be used All techniques for formulation and application of the fungicides are known »

The percentages based on the weight of fungicide may vary according to the type of use of the agent and the specific type of formulation. In general, the fungicidal agent has 0.5-95 % of toxicant.

The fungicides may be formulated and applied with other active ingredients including other fungicides, insecticides, nematocides, bactericides, plant growth regulators, fertilizers, etc.

embodiment

The preparation and the fungicidal activity of the compounds according to the invention are illustrated by the following examples.

EXAMPLE 1

Preparation o f 3- (N- Chlq r ace tjyl -] ~ 2 ^?

iton

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A solution of 10 g (0.055 mol) of o <bromo jf -butyrothiolacton, 668 g (0.055 mol) of 2,6-Dimethy aniline and 5.58 g! (0.055 mol) is DimethyIpyridin to 85-90 ⁰ C. for 12 hours heated. The reaction mixture is then cooled and diluted with water and methylene chloride. The organic phase is separated off and filtered through a short silica gel column. The filtrate is evaporated under reduced pressure to give an oily residue. The residue is washed with 5% hydrochloric acid and then with water. It is then dried over magnesium sulphate to give 7.2 g of 3- (N-dimethyl-phenylamino) - / - -butyrothiolactone. "The infrared spectrum of the thiolactone shows strong carbonyl absorption at 5.88 micron. Elemental analysis of C ₁₂ H ₁₅ NOSj % $% is calculated at 14.5

found 14.2,

A solution of 1.52 g (0.0134 mole) of chloroacetyl chloride in 10 ml of toluene is added dropwise to a solution of 2.97 g (0.0134 mole) of 3- (N-dimethylphenylamino) - y -butyrothiolacton added in 100 ml of benzene The reaction mixture is heated at the reflux temperature until hydrogen chloride gas evolution is complete (about 3 hours), then cooled and evaporated under reduced pressure to give a brown solid. After recrystallization from isopropanol'2.5 g of 3- (N-chloroacetyl-W ~ 2,6-dimethylphenylamino) - * · r'-buty.rothiolacton as brown crystals with a mp. 138-139 ⁰ C are obtained. The infrared spectrum of the product shows two strong carbonyl absorption bands at 5.88 and 6.02 / u. The product is listed in Table A ^- as compound A-1.

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give.

EXAMPLE 2

Preparation of 3- (N-chloroacetyl-N -2 - chloro-6 * - me thylphenylamino) - f h -butyrot iola CTON

A solution of 8 g (0.044 mol) of o -bromo- r- butyrothiolactone, 6.23 g (0.044 mol) of 2-chloro-6-methylaniline and 4.7 g (0.044 mol) of 2,6-dimethylpyridine become about 16 Heated at about 95 C under a nitrogen atmosphere. The reaction mixture is then cooled, diluted with 60 ml of methylene chloride, washed with water and then with 10% hydrochloric acid and finally filtered. The filtrate is dried over magnesium sulfate and evaporated under reduced pressure to give a dark viscous residue. The Rücketand is eluted chromatographically over a short silica gel with dichloromethane. The fractions containing the product are evaporated to give 4.59 g of 3 ~ (N ~ 2 ~ Chlqr-6-methylphenylamino) -Γ-butyrothiolactone. Thin layer chromatography of the product shows a large spot. The infrared spectrum of the product shows strong carbonyl absorption at 5.88 / i and the MR spectrum shows a methyl 3-proton singlet at 2.33 ppm (based on tetramethylsilane).

A solution of 2.15 g (0.019 mol) of chloroacetyl chloride in 10 ml of toluene is added dropwise to a refluxing solution of 4.59 g (0.019 mol) of 3- (N-2-chloro-6-methylphenylamino) - ' "-butyrothiolactone in 150 ml of toluene was added The reaction mixture is heated at the reflux temperature for 7 hours to produce HCl glass

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is stirred. About 16 hours at 25 ⁰ C and then evaporated under reduced pressure to give a dark residue. Thin-layer chromatography. of the residue shows two spots. The residue is chromatographed on a silica gel column with acetone / methylene chloride as the eluent. The chromatograph! View fractions containing the product second in elution from the column are combined and evaporated to give the desired product. After crystallization from isopropyl alcohol 0.98 g brown solid with a mp be. 133-137 ⁰ C received. The infrared spectrum of the product shows two strong carbonyl absorption bands at 5.84 and 5.95 / u. The compound is given in Table A as compound A-3.

EXAMPLE 3

Preparation of 3- (N-Methox ~ N ylmethyl-2 6 _-? Dim ethylphenylamino) - K-butyro thiola CTON

A solution of 1.46 g (0.0135 mol) of methoxyacetyl chloride in 10 ml of methylene chloride is added dropwise to a refluxing solution of 3 g (0.0135 mol) of 3- (N-2,6-dimethylphenylamino) -. the butyrothiolactone is refluxed for three hours and then evaporated to give a solid. The solid is recrystallized from a mixed solution of ether: benzene: hexane (10: 1: 10). give 1.8 g of product as a tan solid of mp. 86-87 ⁰ g are obtained. the infrared spectrum of the product shows two strong Carbonylabsorptionsbanden at 5.85 and 6.03 / i. the product is

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in Table A as Compound A-4.

EXAMPLE 4

Preparation of 3- (N-chloroacetyl 1-17-2,6- dimethyphenylamino) -5- chloro - F- butyro lactone

A slurry of 16 g (0.06 mole) of 3- (K-chloroacetyl-l-2,6-dimethylphenylamino) - r-butyrolactone, 11 g (0.08 mol) of H-chlorosuccinimide and 0.5 g of benzoyl peroxide in 200 The carbon tetrachloride is refluxed for 18 hours. The reaction mixture is then cooled to about 25 ⁰ C, wherein a pesticide separates. The pesticide is filtered from the reaction mixture and washed with 200 ml of methylene chloride. The mother liquor is washed with water, dried over magnesium sulfate and evaporated under reduced pressure to obtain an oily residue. The residue is crystallized from ether, giving 19 »5 g of product, mp 103-106 ⁰ C are obtained. This product is shown in Table B as Compound B-1. ,

EXAMPLE 5

Preparation of 3- (N-acetoxyacetyl- II-2,6 -diiae-1-yl - phenylamino ) - * - / - "- butyrolactone

A 13.7 g (0.1 mol) sample of acetoxyacetyl ^; Chloride is added dropwise to a solution of 20.5 g (0.1 mol) of N-2,6-dimethyl-phenylamino- r- butyrolactone and 7.9 g (0.1 mol) of pyridine in 150 ml of benzene. After the addition, the reaction mixture is stirred for about 4 hours at 25 ° C, then washed with water, dried over magnesium sulfate and under reduced pressure

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evaporated to give an oily residue. The residue is crystallized from ethyl ether / hexane to give 27.3 g of product, mp. 90-91 ⁰ C. This product is shown in Table B as Compound B-2.

EXAMPLE 6

Preparing o n _{N-hydroxyacetyl-N-2,6-:}

dimethy 1- phenylamine o-i- butyrolactone n

A solution of 50 g (0.18 mol) of 3- (N-chloroacetyl-N ~ 2,6-dimethylphenylamino) -r'-butyrolactone, 14.5 g (0.36 mol) of sodium hydroxide, dissolved in 50 ml of water is, and 450 ml of dimethoxyethane is stirred for 16 hours at about 25 ⁰ C. The resulting reaction mixture is filtered and diluted with 500 ml of methylene chloride. Hydrogen chloride gas is bubbled through the reaction mixture for one hour, which is then filtered, dried over magnesium sulfate and evaporated under reduced pressure. The residue obtained is washed with 10 % ethyl ether / 90 % hexane, filtered and air dried. There are obtained 36.5 g of product as a white crystalline pesticide, mp. 173-174 ⁰ O. The product is given in Table B as Compound B-3. "

EXAMPLE 7

Preparation of H-ethoxyacet; yl ~ H-2 _t 6-d ime thy 1 phe ny 1 ami no -i / ^ -bu ty r ο la ct on

A 6.2 g (0.05 mole) sample of ethoxyoacetyl chloride is added dropwise to a refluxing solution of 10.3 g (0.05 mole) of 3- (N-2,6-dimethylphenyl).

t - 24

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amino) - y-butyrolaeton in 150 ml of toluene. Thereafter, the reaction mixture is heated under reflux for a further two hours, after cooling, the reaction mixture is washed with water, saturated sodium bicarbonate solution and with water, dried over magnesium sulfate and evaporated. There are 11.2 g of 3- (N-ethoxyacetyl-N-2,6-dimethylphenylarnino.) - Y-butyrolactone, mp 73-75 ⁰ C obtained. The product is recorded in Table B as Compound B-9.

EXAMPLE 8

Preparation of N- methylthioacetyl-N-2,6-dimethylphenylamino- j- butyrolactone

A 22 g (0.3 mol) sample of sodium methylmercaptide is added in small quantities to a solution of 25.3 g (0.08 mol) of N- (bromoacetyl-N-2,6-dimethylphenylamino) - '/' -butyrolactone from pp. 116-117 ⁰ C in 200 ml Dimethy1-sulfoxide given a mild exothermic reaction takes place. The reaction mixture is allowed to stir for about 16 hours at about 25 ° C. It is then heated to about 150 ⁰ C under water jet vacuum to remove a portion of the dimethyl sulfoxide solvent. The residue is diluted with water and the aqueous layer is separated. The organic portion is dissolved in 35 ml of methylene chloride, washed with water, dried over magnesium sulfate and evaporated under reduced pressure to give an oil. This oil is on a "silica gel column (eluent: 20% acetone / 80% petroleum ether) to give the product (11 g) is obtained, which melts after crystallization from Ethylgther / acetone at 77-78 ⁰ C. This product is in. ·Table

1-25 -

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B as compound B-6.

EXAMPLE 9

Preparation of 3 - (N -chloroacetyl-N-2-methyl ~ naphth-1-ylamino) - y-butyrolactone

In a 200 ml round bottomed flask equipped with a heating jacket and connected to a water jet vacuum system, 15 g (0.1 mole) of "1-amino-2-methylnaphthalene, 16.4 g (0.1 mole) ζ <are added J ^ -bromo-butyrolactone and 10.7 g (0.1 mol) of 2,6-Dirnethylpyridin. heat the reaction mixture at about 94-101 ⁰ C and 160 mm · Hg for about 7 hours. the reaction mixture is The filtrate was concentrated under reduced pressure to give an oily residue, which was then eluted on a silica gel column with 15% acetone / 85 % petroleum ether. obtained N-2-methylnaphth-1-ylamino) butyrolactone from Pp 92-94 ⁰ C. Elemental analysis of C ₁₅ H ₁₅ HO _2..:

⁰ ZoC ₁ calculated 75.0, found 74.5; % H, calculated 5.9, found 5.6; % U, calculated 5.8, found 5.6. "

A 2.4 g (0.021 mol) sample of chloroacetyl chloride is added to a refluxing solution of 5.0 g (0.021 mol) of 3- (N-2-methyl-naphth-1-ylamino) -butyrolactone in 100 ml of toluene given. The reaction mixture is heated at reflux for 30 minutes. Gas is generated during the reflux for 30 minutes and a white precipitate is formed. Thereafter, the reaction mixture is cooled, washed with water, over

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Dried magnesium sulfate and evaporated under reduced pressure to give 4 »3 g of product as a white solid, mp 121-122 ⁰ C are obtained. The infrared spectrum of the product shows two strong carbonyl absorption bands at 5.62 and 5.88 / U- . The product is given in Table C as Compound C-1.

EXAMPLE 10

Preparation of 3- (N-methoxymethyl -N-2- methylnaphth-1-ylamino) -γ * -butyrolactone

A 2.4 g (0.022 mole) sample of methoxyacetyl chloride is added dropwise to a solution of 5.5 g (0.022 mole) of 3- (N-2-methyl-naphthyl-1-yl-amino) - / - butyrolactone and 1 , 7 g (0.022 mol) of pyridine in 100 ml of methylene chloride. The reaction mixture is stirred for one hour at about 25 ⁰ C and then heated under reflux for about 6 hours. Then allowed to cool for 16-18 hours. The reaction mixture is washed successively with water, saturated sodium bicarbonate solution and water, dried over magnesium sulfate and evaporated under reduced pressure. The residue obtained is chromatographed on a silica gel column. The EIuierung with 25% acetone / 75% petroleum ether gave 4.3 g of product, mp. 42-46 ⁰ C. The product is shown as compound C-2 in Table C.

The other compounds given in Tables A, B and C are prepared by methods similar to those given in Examples 1-10. The structures of each compound given in Tables A, B and C are by the KMR spectroscopy and / or

1 - 27 -

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IR analysis confirmed. , · .. '

EXAMPLE · 11

Preventive control of tomato rot (late blight)

The compounds of the invention are tested for their preventative control of Phytophthora infestans, which produces tomato blight (late blight). 5-6 weeks old Bonny Best tomato seedlings are used. The tomato plants are sprayed with a 250 ppm suspension of the test compound in acetone, water and some non-ionic emulsifiers "The sprayed plants were then inoculated 1 day later .with the organism, placed in an environmental conditions corresponding chamber and at 19-20 ⁰ C and 100 incubated% relative humidity for at least 16 hours' iTach incubation, the plants are kept for about 7 days in a greenhouse at 60-80% relative humidity. The percent control of disease caused by a particular test compound refers to the percent reduction in disease relative to untreated plants. The results are given in Table I. In Table I, the test concentrations are given in 250 ppm unless otherwise indicated by the numbers in the parentheses.

EXAMPLE · 12

Eradicating tomato blight (late blight)

Several compounds of the invention are contrasted with respect to their eradicating control properties

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Phytophthora infestans, which produces the late blight. 5-6 week old tomato plants (variety Bonny Best) are used. These tomato plants are inoculated with the organism, placed in an environmental chamber and at 18 - 22 ⁰ C and 100 % relative humidity for two days. incubated. Subsequently, the plants are sprayed with a 250 ppm suspension of the test compound in acetone, water and about nonionic emulsifier. The sprayed plants are allowed to dry. They are then at 18 - 22 ⁰ C and held for 95-100% relative humidity in a greenhouse. Ten days after vaccination, the plants are examined for fungal infections. The proportion of disease control caused by a particular test compound is based on the rate of disease reduction relative to untreated control plants. "The results are shown in Table I. In Table I, the test concentration is 250 ppm unless indicated by other numbers in the parentheses.

EXAMPLE 13

Preventive control of fawn down mildew on the Weinre ( Downy Mildew)

The compounds of the invention are tested for control of downy mildew on grapevines, which is due to Plasmopara viticola. Distant leaves between -70 and 85 mm in diameter of 7-week-old Emperor grapevine seedlings of the Vita vinifera family are used as host plants. The

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Leaves are sprayed with a solution of the test compound in acetone. The sprayed sheets are 'dried, inoculated with a spore suspension of the organism, placed in a moist chamber and corresponding environmental conditions at 18 - 22 ⁰ C and incubated for about 100% relative humidity. 7-9 days after vaccination, the degree of disease control is determined. The percent disease control level produced by a particular test compound refers to the percent disease reduction relative to untreated test plants. The results are given in Table I.

EXAMPLE 14

From rotten control of downy mildew on wine (Downy Mildew)

The compounds of the invention are tested for their eradicating pesticidal powdery mildew control on grapevines, which is due to Plasmop ara viticola. Distant 70-85 mm diameter leaves of 7-week-old Vitis vinifera Emperor seedlings are used as host plants. The plants are inoculated with the organism and placed in an environment appropriate chamber. They are incubated there at 18-22 ⁰ C and about 100 % relative humidity for two days. Subsequently, the leaves are sprayed with a solution of the test compound in acetone. The sprayed sheets are then maintained at 18-22 ⁰ C and at about 100% relative humidity. 7-9 days after vaccination, the level of disease control is determined. The process

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Tual disease control produced by a particular test compound refers to the proportion of disease reduction relative to non-treated test plants, and the results are shown in Table I.

EXAMPLE 15

Systematic soilwashing treatment; for controlling cabbage or flower rot and root rot on saffron

Compound B-4 (4-methoxyacetyl-TI-2,6-dimethylphenylamino) -butyrolactone) is tested for safener , P. hytophthora cryptogea and Py parasitica in soil dehydration studies against herbaceous or floral or root rot organisms for determining their systemic activity ,

Two week old saffron seedlings are used as host plants. Pots with the seedlings are soaked in an aqueous suspension of the test compound at various test concentrations (four pots / concentration level). One day after the treatment, an incubation product of the organism is poured on the soil surface in the pots. The incubation product was prepared by cultivating the organism in a mixture of oatmeal, potato dextrose and soil. Die.geimpften seedlings are then kept in a greenhouse at a day temperature of 20 - 25 ⁰ C and a ITa cht temp era door 15 - 20 ⁰ C. 3-4 weeks after vaccination, the plant root and the herbaceous / blood are examined for the disease infestation. The percentage control of the disease caused by the test compound relates

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on the percentage reduction in disease relative to untreated test plants. The test concentrations and% nuisance control are given in Table II.

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TABLE A.

Compounds of the formula

CH,

Ar

RJ

pp

2,6- (CH ₃ ) ₂ O

ClCH ₂ 130-131

Elemental analysis

ber. gef. 11.9 13.1

₃₂

2-Cl-6-Ch ₃ O 2,6 (CH ₃ ) 0 2-Cl-6-CH ₃ O 3,4- (Cl) ₂ O

CH ₃ OCH ₂

CH ₃ CO ₂ CH ₂

ClCH ₂

_{2 2} 2,6- (C ₂ H ₅ ) ₂ O ClCH ₂ 2,6- (C ₂ H ₅ ) ₂ OCH ₃ OCH

10.4 31.5 '10 .9

_{252 3} 2,3- (CH ₃ ) ₂ O ClCH ₂

₃ 2,3- (CH ₃ ) ₂ O

CH ₃ OCH ₂

_{3 3} 2-CH ₃ -OC ₂ H ₅ (XClCH ₂

2,3,5,6

ClCH

140-143 57.8 62.4 62.5 57.8 59.0

CH ₃ OCH ₂ .122-123 63.6

₃₄

A-16 2,3,5,6- (CH ₃ ) ₄ O

carbon hydrogen 0 = phenyl 11.7 32.7 12.6

2,6- (CH ₃ ) ₂ OCH ₃ CO ₂ CH ₂ I 24-125 - - ClCH ₂ 133-137 22.3 23.6 86-87 - - 9 * 9-100

oil

108-114 74.-82 99-102

oil

110-120

₃₂ ^ ₃₂ 88-90 2,3,6- (CH _{3) 3} OCH ^ CH _2101-103 2,3,6- (CH _{3) 3/2} 3ClCH IO4-IO7 6

11.9 11.7

57.8 .62.5 -6O.2 ¹ 56.5 ¹

60.T

65.8

7.2

Ar R ¹ s! Pp. C ⁰ table calc. gef. B 0 11 Compounds of 1 CH-R 2 formula N gef. about • X ^ Ef. O ¹ (D ClCH ₂ Cl 103-106 - - "CH- ι calc. - 22-. 4 21st (D CH ₃ CO ₂ CH ₂ H 90-91 63.Ο 63.3 O = C _x - 4.5 - - (D HIGH ₂ H 173-174 63.9 63.2 4.6 4.4 - - (D CH ₃ OCH ₂ H 133-134 65.0 65.5 H Elemental analysis 5.3 5.2 - - O ² (D 0SCH ₂ H 84-86 - calc. 5.1 - 8th. 9 9th 1 ² No, (D CH ₃ SCH ₂ H 77-78 - - - Kef. '  - - 10th 9 9th 1 ¹ B-1 (2) ClCH ₂ H" oil - -. 6.3 - - 9th 2 11th B-2 (2) CH ₃ OCH ₂ H oil 6? .O 66.0 6.5 6.7 - 4.0 - - - B-3 (D CH ₃ CH ₂ OCH ₂ H 73-75 σ 66oO 66.0 6.9 6.6 4o8 5.0 - - - .2 B-4 0 (3) ClCH ₂ H 128-130 - __ - 6.8 4.8 - 11 5 13 B-5 K3) CH ₃ OCH ₂ H ' 1 04-105 66.9 67.5 - - - .4.5 - - .: B-6 2 (1) 1-C ₃ H ₇ OCH ₂ H- oil 66.9 66.9 - - 4.6 4.1 - B-7 3 (1) ClCH ₀ br 98-102 46.6 47.7 7.2 - 4.6 4.2 - - __ B-8 7.3 7.2 3.9 B-9 - 7.2 B-1 7.5 - B-1 7.6 7.5 B-1 4.2 7.5 B-1 4.4

Table B (continued)

(1) 2,6- (CH ₃ ) ₂ ) 0

(2) 2,3,6- (CH ₃ ) ₃ O

(3) 2,3,4,5- (CH ₃ ) ₄ O.

chlorine

² sulfur

Table C - Compounds of the formula

tt

.CR ¹

Ar-IT;

-F ^H 2

¹ O '

CE

Ir. Ar R ¹ Mp. ⁰ C C over. gef. calc. gef. about A • / gef , C-1 (D ClCH ₂ 121-122 - - - - C-2 (1) CH ₃ OCH ₂ 42-46. • 69.0 72.6. 6.1 606 4th 5 4th 5 C-3 (D BrCH ₂ 116-118 - ~ - - - - C-4 (D CH ₃ SCH ₂ 52-55 65.6 62.3 5.8 5.4 - - C-5 (2) ClCH ₂ 110-113 63.3 63.3 4.7 4.8 4 ' 6 4th 5 0-6 - (2) CH ₃ OCH ₂ 109-111 68.2 69.6 5.7 5.9 4th 7 5th 3 (D 1- (2-methylnaphthyl) (2) 1- (Uaphthyl)

Elemental analysis

calc.

11.2

12.5 (Cl)

22.1 21.5 (Br)

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TABLE I

, · Combat tomato blight (Late Blight)

Palscher Mehltau d.Weinrebe

ffr. Preventive 0 exterminating Preventive exterminating (Ppm) (Ppm) (Ppm) (Ppm) A-1 98 84 (100) 82 (40) 5 (100) A-2 14 - 3 (100) A-3 100 42 (100) - 7 (100) A-4 96 (40) 81 (100) 98 (100) 10 (100) A-5 29 - -. 0 (100) A-6 23 * __ 0 (100) A-7 98 54 93 (16) 80 (16) A-8 26 (100 __ 0 (100) A-9 68 (40) _- ~ _ 12 (100) A-10 89 (100) 95 -.- 80 (100) A-11 80 - - __ A-12 89 __ __ A-13 100 __ -_. __ A-14 100 -_. __ A-15 37 -_ A-16 100 __ - , - B-1 100 92 (100) 0 (100) 88 (100) B-2 88 __ - - 9 (100) B-3 92 (100) 92 (100) - ~ 0 (100) B-4 88 (16) 96 (40) 100 (40) 95 (16) B-5 84 58 73 (100) B-6 97 96 - 54 (100) B-7 77 - __ ' - B-8 100 93 (100) .--  - B-9 • 97 __ - B-10 • 37 -. · B .11 100 -_ B-12 95 __ __ __ C-V 100 55 (100) 96 (16) 84 (16) C-2 __ __

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TABLE II

Combating cabbage or flower rot and • Conc. Bodenwässerune; 100 100 Root rot in saffron α Standard ⁺⁺ (5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole) ppm % Combat 97 100 ⁺ 40 98 78 17 connection 16 Compound B-4 100 40 16 P. Crvptogea P. parasitica 98 78 14 78 12 0

100 ppm = 50 micrograms / cm ²

US Patent No. 3,260,588 ^f s and 3 x 260,725

Claims (3)

Claim . 1. A process for the preparation of 3- (N-ACYL-Ji-ARYLAMIM)) - BUTYROLACTOinSN or - f -BUTYROLA C TOFjEU of the general formula I. CH-R ² wherein Ar is a phenyl or Naphthyl optionally identical or different with fluoro, chloro, bromo, alkyl groups having 1-4 carbon atoms or alkoxy groups R 1 is a hydroxymethyl group, a halomethyl group having 1-3 * identical or different fluorine, chlorine or bromine atoms, an alkoxymethyl group having 1-6 carbon atoms, alkylthiomethyl group having 1-6 carbon atoms, phenylthiomethyl group, Phenoxymethyl group, a phenylthiomethyl or phenoxymethyl group., Which on the phenyl ring with 1 or 2 fluorine atoms. Chlorine atoms, bromine atoms, alkyl groups with 1-4 carbon atoms or alkoxy groups with 1-4 carbon atoms R is a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1-6 carbon atoms, or a phenyl ν - 10.4.1979 ... APC07D / 208 54.459 12 is optionally substituted identically or differently with 1 or 2 fluorine atoms, chlorine atoms, bromine atoms or alkyl groups having 1-6 carbon atoms ", and Y represents an oxygen atom or a sulfur atom with the proviso that Y is not an oxygen atom when Ar is a Phenyl group or a substituted phenyl group and R is a halomethyl group, characterized in that an aniline of the general formula VIII ₂ (VIII) with a <ς><-halo / "butyrolactone or o <halo-y butyrothiolacton the general formula IX X-CH CH-R ^£ (IX) alkylated and then the <> <- (IT-arylamino) -butyrolactone or -butyrothiolacton of the general formula X. Ar-MH-CH CH ₀ I (D. O = C. .CH-R ² Y (X) 10.4.1979 APC07D / 208 7β1 54 459 12 with an acyl halide of the general formula U 0 d XCR ¹ (XI) 12 acylated, wherein Ar, R, R and Y are as defined above and X is the chlorine or bromine atom.